Vinyl chloride polymers plasticized with mixed morpholides of dimerized fatty acids



May 10, 1966 F. c MAGNE ETAL 3,250,635 VINYL CHLORIDE POLYMERS PLASTICIZED WITH MIXED MORPHOLIDES OF DIMERIZED FATTY ACIDS Original Filed Feb. 19, 1963 WT.%S

INVENTORS FRANK C. MAGNE EVALD L. SKAU ATTORNEYS ROBERT R. MOD

United States Patent 6 Claims. (Cl. 106316) This application is a division of application bearing Serial No. 260,100, filed February 19, 1963.

A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to unique morpholides. More particularly, the invention provides the morpholides of mixtures of long chain saturated and unsaturated fatty acids and the epoxy and dimer derivatives thereof that can reproducibly be produced from the fatty acids found in natural glycerides. These mixed morpholides are efficient primary solvent plasticizers exhibiting good compatibility with homopolymers and copolymers of vinyl chloride.

A morpholide of an acid is an amide of the acid in which the amido nitrogen atom is a nitrogen atom of a morpholine ring. Prior workers have produced the morpholides and other amides of various individual fatty acids and mixtures of fatty acids. Many of the fatty acid amides heretofore produced, e.g., those disclosed in US. Patents 1,986,854; 2,339,056; and 2,380,925; are solvent plasticizers for hydrophilic vinyl resins, such as the polyvinyl acetal resins.

A compound which is a solvent plasticizer for, and thus is compatible with, a hydrophilic vinyl resin such as a polyvinyl acetal resin, exhibits only a very limited compatibility with a hydrophobic vinyl resin such as polyvinyl chloride. If a resin is plasticized with a compound with which it has only a limited compatibility the plasticizer soon exudes or migrates to the surface unless the plasticizer is used in limited amount, or is used in conjunction with a mutual solvent, to obtain adequate compatibility.

As might be expected from the known compatibility of various morpholides of fatty acids with the polyvinyl acetals, the morpholide mixtures from glyceride oil acids such as cottonseed oil acids or peanut oil acids, although in other respects satisfactory vinyl chloride resin plasticizers, are highly incompatible with polymers of vinyl chloride, even when used as a secondary plasticizer with an equal amount of a highly compatible plasticizer.

Similarly, the morpholide of palmitic acid and the morpholide of stearic acid, though in other respects satisfactory vinyl chloride plasticizers, have been found to be highly incompatible when used as plasticizers for vinyl chloride resins, exhibiting migration to the surface within 36 hours.

The term vinyl chloride resins is used throughoutthe specification and claims to refer to homopolymers and copolymers of monomers containing vinyl chloride in a predominant proportion in parts by weight. Terms such as good compatibility, compatible, and compatible plasticizers in reference to plasticizers for vinyl chloride 3,250,635 Patented May 10, 1966 ice resins are used throughout the specification to refer to plasticizers which show no signs of exudation or migration to the surface for at least 30 days when the plasticizer is present in the proportion of about parts per parts by weight of vinyl chloride resin.

The primary object of the present invention is to provide morpholides which are good primary solvent plasticizers for vinyl chloride resins, and which are plasticizers that can economically be produced from fatty acids obtainable from glyceridic oils and fats.

The morpholides provided by this invention exhibit good compatibility with homopolymers and copolymers of monomers predominating in vinyl chloride, such as polyvinyl chloride, and the vinyl chloride-vinyl acetate copolymers predominating in vinyl chloride. They may be employed as plasticizers in proportions of from 10 to about 70 parts by weight per 100 parts by weight of polymer. Their plasticizing efiiciency is high and the resulting plasticized resins have good thermal and light stability, good low-temperature properties, and a low volatility loss. 1

In US. Patent No. 2,863,845 it was disclosed that the morpholides of mixed saturated and unsaturated vegetable oil fatty acids in which mixtures of acids the weight proportions of saturated acids (S), monoolefinic acids (M), polyolefinic acids (P), and epoxidized fatty acids (E), are such that S/S+M+P+E is from about 1 to 9/100 and P/M+P+E is less than about the value of E being zero when no epoxidized fatty acids are present in the fatty acid mixture, are good compatible plasticizere for vinyl chloride resins. The term epoxidized fatty acids is used to designate C to C alkanoic and alkenoic acids containing at least one epoxy group. Such acids are produced by the epoxidation of at least one olefinic group of an unsaturated fatty acid.

Terms such as dimer acids, dimer acid, or dimerized acids are used indiscriminately to refer to acids or mixtures of acids consisting essentially of dib asic acids containing from 32 to 44 carbon atoms resulting from the polymerization or dimerization of long chain C to C unsaturated fatty acids. The term dimerized cottonseed fatty acids is used to refer to cottonseed fatty acids which have been subjected to dimerizing treatment.

In copending patent application Serial No. 79,470 filed December 29, 1960, now Patent No. 3,066,111, it was further disclosed that the morpholide mixtures obtained by reacting morpholine with mixtures of the fatty acids which occur in selectively hydrogenated cottonseed oil, said morpholide mixtures containing a proportion of saturated, monounsaturated, and polyunsaturated acyls; i.e., acyls obtainable from selectively hydrogenated cottonseed oil, such that the acyls are equivalent to a mixture of acids in which S/S+M+P is about 25/100 and P/M-l-P is less than V are good compatible plasticizers for vinyl chloride resins.

We have now made the surprising discovery that mixtures of morpholides of vegetable oil fatty acids containing a proportion of saturated, monounsaturated, and polyunsaturated acyls such that the acyl mixture is equivalent to a mixture of acids in which P/M+P is much larger than are compatible plasticizers for vinyl resins provided the value of S/S+M+P lies within a specified range which depends on the value of P/M+P and provided also that the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms and that the percentage of saturated acyls containing 18 or more carbon atoms an the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide mixture. For example, as can be seen from the examples and from the sole figure in the accompanying drawing (in which figure, as described below, all compositions within the approximate boundaries of area Mfgc are compatible), morpholide mixtures of saturated, monounsaturated, and polyunsaturated morpholides for which P/ M +P:25/ 100 (represented by the compositions along the straight line joining x and S) are compatible only between i and k;

that is, only if the value of S/ S +M +P lies between about 20/100 and 60/100 and provided also that t-he saturated' acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms,

and that the percentage of saturated acyls containing '18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide.

vinyl plasticizers provided the ratio P/M+P lies within 'a specified range of values and provided also that the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 atoms and that the percentage of saturated acyls containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide mixture. This is surprising since it shows, as can be seen from the drawing, that compatible plasticizers represented by the compositions within area Mfgc can be obtained by mixing (in appropriate proportions) two incompatible plasticizers, e.g., those represented by.

compositions in areas Mrfa and cgS, respectively.

We have also discovered that mixtures of the morpholides of saturated, polyunsaturated, and epoxidized fatty acids in which S/S+M+P+E is much larger than 9/100 and P/M+P+E is much larger than but which are compatible vinyl chloride resin plasticizers can be made by mixing two incompatible morpholide mixtures, provided that-the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms, and that the percentage of saturated acyls containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide mixture. For example, the composition represented by Example 43, for which P/M+P+E=about 35/ 100 and the composition represented by Example 40, for which S/S+M+P+E=about 75/100 are individually incompatible, but a mixture of equal parts of these compositions (Example 46), for which E/E+S=='4/ 100 and E/P+E=72/ l00 is compatible.

The mixed morpholides of this invention comprise mixtures of the morpholides of mixed saturated and unsaturated fatty acids, in which mixture of acids, the weight proportions of saturated acids (S), monoolefinic acids (M), and polyolefinic acids (P), are such that the following conditions are satisfied: (1) that S/S-i-P is greater than about 50/100 (i.e., that the composition lies within area Mes in the drawing), (2) that M/S+M+P is greater than about 30/100 (i.e., that the composition lies within area Mbc), and (3) that P/M+P is less than about 40/100 (i.e., that the composition lies within area 4 Mas), excluding those mixtures which are such that S/S-l-M-l-P is either less than about 9/100 or equal to about 25/100 and P/M+P is less than about (i.e., excluding compositions lying within the area Mrk or on the line ny); provided also that the saturated acyls present in the morpholide mixture are predominantly saturated acyls containing from 12 to 18 carbon atoms, and that the percentage of saturated acyls containing 18 or more carbon atoms in the morpholide mixture amounts to less than about 17% of all the acyls in the morpholide mixture. Thus, the mixed morpholides of this invention comprise compositions represented by all compositions within the area krfgc in the drawing except along ny; that is, the area which is common to the areas MeS, Mbc, and MaS, excluding those within the area Mrk and along line ny.

The morpholides of this invention also include the morpholides of epoxidized fatty acids. They also include the morpholides of mixtures of epoxidized fatty acids with saturated acids and/or polyunsaturated fatty acids .in

which mixtures of acids, the weight proportions of saturated acids (S), epoxidized acids (E), and polyunsaturated acids (P), are such that the following conditions are satisfied: (1) that E/S+E is greater than about /100; (2) that E/P+E is greater than about 70/100; and (3) that the saturated acids present in the mixture of acids are predominantly saturated acids containing from 12 to 18 carbon atoms and the percentage of saturated acids containing 18 or'more carbon atoms in said mixture of acids is less than about 17% of all the acids in the mixture.

The morpholides of this invention also include the morpholides of dimer acids. They also include the morpholides of acid mixtures consisting essentially of dimer acids (D), monounsaturated acids (M), and saturated acids (S) in which mixtures of acids either (1) the weight proportion of S is less than about /100 or (2) the weight proportion of M is greater than about 10/100 and the weight proportion of S is between about 55/100 and 70/ 100.

While the morpholides of this invention can be produced in a variety of ways, they are preferably produced by reacting the mixed acids with morpholine. The mixed acids are preferably produced by saponifying a natural glyceride, acidifying the resulting salts and, if necessary, adjusting the composition of the resulting acid mixture so as to obtain a suitable composition which when reacted with morpholine will result in a compatible plasticizer (1) by known procedures for reducing the proportion of saturated acyls such as fractional crystallization or distillation, and/ or (2) by converting polyunsaturated acyls to monounsaturated acyls, epoxyalkenoic acyls, or epoxyalkanoic acyls-the corresponding morpholides of which are themselves compatible plasticizerssuch as by hydrogenation, halogenation, formylat ion, dimen'zation, or epoxidation,

etc., and/or (3) by admixing with other fatty acid mixtures and/ or with pure fatty acids. Alternatively, the fractionation, hydrogenation, epoxidati-on or mixing, etc., may be performed on the materials separately or combined which are capable of yielding the desired acid composition or on the corresponding morpholides or mixed morpholides. In general, it is usually preferred to perform epoxidation at the morpholide stage.

The necessary adjustment can readily be deduced from the drawing and from a knowledge of the proportions of S, M, and P acyls in the given mixture as determined by standard analytical procedures. For example, consider a mixture of vegetable oil fatty acids in which the weight proportions are such that S/S+P is about 35/ P/M+P is about 65/100; M/S-l-M-j-P is about 25/100; and in which the predominant saturated fatty acid is the C acid with very small amounts of the C and C acids. The drawing shows that the mixed morpholides made from this mixture (represented approximately by 14 in the drawing) would be incompatible. The drawing also shows that this mixture of fatty acids can be readily converted to a suitable mixture of acids (i.e., to a composition represented by points within area Mfgc), which when reacted with morpholine will result in a compatible plasticizer; for example, by converting some or all of the polyunsaturated acyls to monounsaturated acyls by such procedures as hydrogenation, halogenation, formylation, dimerization, maleination etc., so that S/S-t-P is greater than about 50/100; M/S+M+P is greater than about 30/100, and P/M-i-P is less than about 40/100.

The composition of the morpholide mixtures of this invention which contain no epoxidized acyls are representcd by all compositions within the area Mfgc in the drawing; that is, within the area bounded approximately by M fg, and gc. The boundaries Mf, fg, and gc are only approximate. Thus the composition of Example which lies near the boundary outside this area is compatible. Slightly incompatible compositions lying close to but outside the boundaries Mf, fg, and gc and even less compatible compositions may be used satisfactorily as primary plasticizers in polyvinyl chloride resin formulations containing lower percentages of plasticizer and/ or as secondary plasticizers admixed with a suitable compatibilizing plasticizer such as the morpholide of epoxidized fatty acids or compatible mixtures of the morpholides of epoxidized fatty acids and/or monounsaturated fatty acids and/ or polyunsaturated fatty acids and/ or saturated fatty acids. Similarly incompatible morpholide mixtures containing the morpholides of epoxidized fatty acids can be used as secondary plasticizers with compatible morpholide compositions which lie within the area Mfgc in the drawing.

The proportion of the saturated fatty acyls having 18 or more carbon atoms in the chain which can be present in the saturated acyl fraction without causing incompatibilty will vary with the overall composition of the morpholide mixture, particularly, the relative proportions of saturated, monounsaturated, and polyunsaturated acyls present in the mixture. It can be determined for a given overall composition by evaluating the performance of a series of samples which differ only in the proportion of the C or longer-chain saturated fatty acyls in the saturated fatty acyls present.

We have also discovered that the morpholides of epoxidized fatty acids, i.e., of C to C alkanoic or alkenoic acids containing at least one epoxy group, are compatible, highly efiicient, primary plasticizers for vinyl chloride resins and impart to the plasticized resin a high degree of stability against heat and light. They are efiicient stabilizers for vinyl chloride resins. We have also discovered that'morpholide mixtures such as can be made by mixing even as much as about one part of the morpholide of palmitic acid with one part of the morhpolide of epoxidized fatty acids or by mixing as much as about 3 parts of the morpholide of polyunsaturated fatty acids with 7 parts of the morpholide of epoxidized fatty acids are also compatible vinyl chloride resin plasticizers and have the advantage that the plasticized resin has increased thermal stability.

Morpholide mixtures which can be prepared by mixing in any proportion any of the compatible morpholide compositions within the area Mfgc in the drawing with either the morpholides of epoxidized fatty acids or with any mixture of morhpolides of fatty acids containing the morpholide of epoxidized fatty acids which mixture of morpholides is itself a compatible vinyl chloride plasticizer are also compatible vinyl chloride plasticizers imparting good thermal stability to the resin. In making such compatible morpholide mixtures the morpholides of epoxidized fatty acids may be introduced by addition or they may be formed in situ; for example, by epoxidizing some of the morpholides of the monounsaturated or polyunsaturated fatty acids in a given morhpolide mixture.

We have also discovered that the morpholides of dimer acids are compatible, etiicient, and permanent primary plasticizers for vinyl chloride resins and that the molded resins plasticized with such morpholides show a surprisingly low volatility loss. More surprising is the fact that essentially zero volatility losses are also obtained when the dimer acid morpholide is mixed with its own weight of another plasticizer which plasticizer when used alone would impart a moderately high volatility loss. The morpholide of dimer acids can therefore be used in conjunction with other more volatile platsicizers to eliminate or reduce volatility loss.

Conversely a particular plasticizing property of the morpholides of dimer acids, such as low-temperature properties, can be improved by using said morpholides in admixture with other appropriate plasticizers which excel in this property. Improved light stability and thermal stability can be attained by inclusion of suitable stabilizers and/or antioxidants in the resin-plasticizer formulation.

Vinyl chloride resins plasticized with the morpholides of dimer acids also exhibit the desirable property of low soapy water extractability. They are also useful for reducing the soapy water extractability of other more highly extractable plasticizers when used in admixture with such plasticizers.

We have also discovered that all mixtures of the morpholide of dimer acids (MD), the morpholide of oleic acid (MO), and the morpholide of palmitic acid (MP), in which the weight fraction of MP is less than about 0.55 and also those mixtures in which the weight fraction of MO is greater than 0.10, and the weight fraction of MP is between 0.55 and about 0.70 are compatible plasticizers the more important plasticizing characteristics of which can be predicted approximately from those of the individual morpholides and their weight proportions in the given mixture.

Morpholide mixtures which can be prepared by mixing in any proportion any compatible morpholide mixture containing the morpholide of dimer acids with either the morpholide of' epoxidized fatty acids or with any mixture of morpholides of fatty acids containing the morpholide of epoxidized fatty acids which mixture of fatty acids is itself a compatible vinyl chloride plasticizer are also compatible vinyl chloride plasticizers imparting good thermal stability to the resin.

The following examples numbered 1 through 68, the data for which are listed singly in tabular form but which may be considered individually or in related groups for discussion purposes, will demonstrate several of the manifold expressions of our invention.

Various morpholide mixtures were tested as plasticizers for vinyl chloride-vinyl acetate (-5) copolymer resin (Vinylite VYDR) in a standard formulation comprising: 63.5% of Vinylite VYDR, 35% plasticizer, 0.5% stearic acid, and 1.0% basic lead carbonate. This formulation for each morpholide sample was milled, molded, and tested. In all examples, the sample was rated as incompatible if the molded stock showed any evidence of exudation or migration to the surface during a shelf storage of 30 days.

The morpholide mixtures used in Examples 1 to 19 were ternary compositions prepared by mixing appropriate proportions of the morpholide of oleic acid, the

morpholide of linoleic acid, and the morpholide of palmitic acid. The approximate compositions and the results of the compatibility test for these samples are given in Table I and plotted as points in the ternary weight-composition diagram in the drawing. In the drawing compatible morpholide mixtures are represented by open circles and incompatible mixtures by black circles. In Table I, M, S, and P represent the weight percent of the morpholides of oleic, palmitic, and linoleic acids comprising the morpholide mixture, respectively.

Table I ture, in which morpholide mixture, the saturated acyls containing 18 or more carbon atoms amount to less than M. S, P, Conn about 17% of all the acyls in the morpholide mixture. Ex. perperper- M/S+M+P PIM+P SIS-+1 path N0. cent cent cent; bility r a Table II 00.5 38.1 1.3 51/100 2000 97/100 fig 1.1 51/100 2/1 0 tag/ 00 8 6.8 79 100 1 0 00 M s P, 71.4 19.2 9.3 71 100 12 100 07/100 0 5 W1 -5 8 1 51/100 0 N0. perperper- M/S+M+P PIM+P s/s+1 01111 37.2 61.9 0.8 37/100 2/100 09/100 0 cent cent Cent 45.0 38.4 10.5 45/100 27/100 70/100 0 0 115.0 12.3 40/13 21/100 77/100 8 .2 21.5 35,1 38100 67100 2( 30 5g 3 3 101 21100 1100 26.3 57.4 16.1 /100 38/100 78/100 C 43 44 3 431190 145100 32, 0 8 3.8 24.2 2 .9 54/100 29/100 5 C 69.4 7.5 23.0 09/100 /100 25/100 I 6315 64/10n 21/100 53/100 9 23- 72.2 15.3 11.5 72/100 14/100 59/100 0 70.0 11.2 18.8 70/100 21/100 37/100 I 3'2 133 53' 173 i i/ "24188 8 15 .6 31 0 100 6 1 C: 15 ;1=1 1 45.3 40.1 14.0 /100 24/100 73 100 0 Comm 1 e nmmpan 6 $813 212 0/ 3 1 21 2 /10 a 1 0 2,1 9, 25.0 715 0.4 25/100 2/100 00/100 1 The physical properties of the Vmyhte VYDR resin plasticized with the morpholide mixtures of Examples 1 C=compatible; I=incompatib1e. 20 20 to 23 are shown in Table III.

Table III Example I Tensile 100% Elonga- Brittle Yola- Compati- No. Plasticize, Morpholide oi- Strength, Modulus, t10n,per- Point, tihty bihty p.s.i. p.s.1. cent C.

11' a 2 040 1,300 400 0.02 c. fiii n i 5 01 21 2... 2950 1,370 500 -34 0.35 o. Rapeseed oil acids--- 3,030 1,470 400 53 1.00 1. Adjusted rapeseed oils. 2,880 55 0- Epoxyoleic acid 3,030 Li 36 --10 0. 41 C. Epoxystearic acid 2, 850 1,500 350 28 0.54 G. Diepoxystearic acidi 2,050 1,330 350 16 0 49 G.

P -11' o'idize cotton- 2223 1 3 3 2,010 1,210 400 20 0.73 0. Full e oxidized cotton- 1 C compatible; I=ineompatib1e.

The sample used in Example 20 was the morpholide of animal type acids, that is, a mixture of fatty acids having the following composition: 10% myristic, 43% palmitic, 9% stearic, 30% oleic, and 8% linoleic acids.

The sample used in Example 21 was the morpholide of animal acids, thatis a mixture of fatty acids having the following composition: 2% myristic, 26% palmitic, 16% ste aric, 48% oleic and 8% linoleic acids.

The morpholide of rapeseed fatty acids used in Example 22 was prepared from the composite fatty acids which were obtained by saponification and acidification of rapeseed oil and which consisted of approximately 9.6% linolenic acid, 13.3% linoleic acid, 20.4% oleic acid, 49% erucic acid, and 7.6% saturated fatty acid. The resulting morpholide mixture, for which the composition was such that M/S+M+P=69/ 100, P/M+P= 25/ 100, and S/S-}-P=25 100, was tested as a plasticizer for vinylite VYDR resin and was incompatible.

The morpholide sample of Example 23 was made by adjusting the composition of the morpholide mixture of Example 22. The latter was mixed with an equal part by weight of a morpholide mixture the composition of which was such that M/S+M+P=a-bout 75/ 100, P/M+P=about 0 and S/S+P=about 100/100, resulting in a final mixture for which M/S+M+P=about 72/100; P/M+P=about 14/100 and S/S+P= about 59/100. This was found to be a compatible plasticizer for Vinylite VYDR resin.

The compositional data for the morpholide mixtures of Examples 20m 23 are given in Table II in which Table M, S, and P, represent the weight percent of the morpholides of monoolefinic, saturated and polyoleiinic fatty acids, respectively, comprising the morpholide mix- The corresponding data for Examples 24 to 2-9 are given in Tables III and/ or IV. For these samples, M, E,- S,

and P represent the approximate weight percent of morpholides of monoolefinic (unepoxidized), epoxidized, saturated, and polyunsaturated acids, respectively, comprising the morpholide mixtures, in which morpholide mixtures the saturated acyls containing 1 8 or more carbon atoms amount to less than about 17% of all the acyls in the morpholide mixture. The morpholide samples of EX- amples 24 and 26 were prepared from the morpholide of linoleic acid and that for Example 25 from the morpholide of oleic acid by epoxidization with perbenzoic or peracetic acid. The morpholide samples of Examples 27 and 28 were prepared by epoxidation of the morpholide of cottonseed oil fatty acids to an oxirane content of 2.62% and 4. 07% i.e., to an extent equivalent to that necessary to epoxidize about 40% and about respectively, of the total number of double bonds present.

The morpholide sample of Example 29 was prepared by mixing the proper proportions of the morpholide mixture of Example 28 and the morpholide of selectively hydrogenated cottonseed fatty acids. The plasticized resin had a specially high degree of thermal stability.

The morpholide mixtures used in Examples 30 to 36, for which the compatibility data are given in Table IV, were prepared by mixing the proper proportions of the morpholides of oleic acid, epoxyoleic acid, and palmitic acid.

The morpholide mixtures used in Examples 37, 38, 39, 40, 41, 42, and 43 were binary compositions prepared by mixing appropriate proportions of the morpholide of epoxy oleic acid with either the morpholide 'of linoleic acid or with the morpholide of palmitic acid. The morpholide mixtures used in Examples 44, 45, and 46 9 were ternary mixtures consisting of equal parts by weight of the mixture used in Example 40 and those used in Examples 41, 42, and 43, respectively. The compositions and the results of the compatibility tests for these samples are given in Table IV. The sample of Example 46 was a compatible vinyl chloride plasticizer though it was made by mixing the samples of Examples 40 and 43 both of which were incompatible.

The sample of Example 47 was the morpholide of the mixture of acids comprising about 75% of dimer acid, 22% of trimer acid, and 3% of monomer. The morpholide was prepared by refluxing the acids with an excess of morpholine in an apparatus equipped with a Dean- Stark t-rap until the evolution of water ceased, using benzene as the entraining liquid. The reaction mixture was taken up in commercial hexane, washed successively with dilute hydrochloric acid and water, and dried over anhydrous sodium sulfate. Free .acid was removed by percolating the hexane solution through a column of activated alumina and eluting the morpholide with a 1:1 hexaneethanol mixture. The solvent was removed by stripping under reduced pressure. The product was acid-free and had a nitrogen content of 3.87%.

The sample used in Example 48 was the morpholide of a trimer-free dimer acid. The morpholide was prepared by the same procedure as described in Example 47. The product was acid-free and had a nitrogen content of 3.90%.

Table IV Ex. No. M E S P E/E-l-S E/P-l-E Compatibility v 100 0 0 100/100 100/100 C. 0 100 0 0 100/100 100/100 C. 0 100 0 0 100/100 100/100 C. 50 25 0 100/100 100/100 C. 0 75 25 0 75/100 100/100 C. 61 6 27 6 75/100 100/100 0. 0 60 0 60/100 100/100 C. 0 55 0 /100 100/100 0. 0 45 55 0 45/100 100/100 I. 20 30 50 0 45/100 100/100 C. 17. 7 26. 8 55. 5 0 45/100 100/100 0. 15 23 62 0 45/100 100/100 0. 12 18 70 0 45/100 100/100 0. 0 40 0 40/100 100/100 I. 0 35 0 35/100 100/100 I. 0 30 0 30/100 100/100 1. 0 25 0 25/100 100/100 I. 0 75 0 25 100/100 75/100 C. 0 70 0 30 100/100 70/100 C. 0 05 0 35 100/100 05/100 I. 0 5O 37. 5 12. 5 57/100 /100 C. 0 47. 5 37. 5 15 56/100 76/100 C. 0 45 37. 5 17. 5 54/100 72/100 0.

1 Compositions containing the morpholidcs of both monounsaturated fatty acids and epoxidized fatty acids, and which can be prepared by mixing appropriate proportions of two morpholide mixtures each of which is a compatible vinyl chloride plasticizer.

2 Compositions containing the morpholides of both monounsaturated fatty acids and epoxidized fatty acids, and which can be prepared by mixing two morpholide mixtures each of which is an incompatible vinyl chloride plasticizer. For example the sample of Example 36 can be prepared by mixing equal parts by weight of two incompatible morpholide mixtures, one consisting of 25 parts of the morpholide of a monounsaturated acid and 75 parts of the morpholide of palmitic acid and the other consisting of 35 parts of the morpholide of epoxyoleic acid and 65 parts of the morpholide of palnitic acid.

' 3 C=compatible: I=incompatible.

Table V Soapy I Tensile Elonga- Brittle Volatility Water Compatilast c zer Strength, Modulus, tion, Point, Loss, Extractbilityl 1 p.S.1. p.s.i. percent percent ability, percent 47 Morpholide of Dimer Acid 3, 670 2, 870 300 +3 0. 0 2- 3 0- (mixed with trimer and monomer). 48 Morpholide of Dimer Acid 3, 430 2, 70 260 +3 0. o c.

(trimer-iree) 40 Hyd C/S Morpholide Dimer 3, 490 2, 300 340 9 0. 0 5. 4 G.

Morpholide (1-3). 50 Hyd C/S Morpholide Dimer 3, 220 1, 890 300 -.-21 0.0 9.0 O.

Morpholide (1-1). 51 Hyd C/S Morpholide Dimer 3, 090 1,570 320 31 0. 41 13. 5 C.

Morpholide (31). 52 Morpholide of Dimerized 0/8 2, 960 1, 590 360 -29 c.

Acids. i

1 C =Compatible; I=Iucompatible.

Table VI MD, MO, MP, Tensile 100% Elonga- Brittle Compati- Example N0. Percent Percent Percent Strength, Modulus, tion, Point, bility 1 p.s.i. p.s.i. Percent C.

0. 0 50. 0 50. 0 2, 880 1, 310 390 33 C. 5.0 90.0 5.0 2, 970 1, 410 370 37 C. 12. 5 75. 0 12. 5 2, 970 1, 450 400 -33 C. 12. 5 12. 5 75. 0 2, 780 1, 350 340 25 I. 25. 0 56. 25 18. 75 3, 080 1, 570 320 31 C. 25. 0 37. 5 37. 5 3, 070 1,590 380 27 G. 25. 0 50.0 25.0 3, 1, 580 370 29 C. 25. 0 25. 0 50.0 3, 1, 660 380 -25 C. 32. 5 32. 5 35.0 3, 120 1,640 400 23 C. 50.0 50. 0 0.0 3, 308 1, 862 375 19 C. 50.0 25. 0 25. 0 3, 240 1,830 400 -19 C. 50. 0 37. 5 12. 5 3, 220 1, 890 300 21 O. 50. 0 0. 0 50. 0 3, 280 1, 930 360 -13 C. 75.0 12.5 12.5 3, 400 2, 320 310 7 C. 75.0 18. 75 6.25 3, 490 2, 290 330 9 O. 0. 0 0. 0 100. 0 2, 530 1, 270 340 27 I.

1 C Compatible; I=1ncompatible.

The samples of Examples 49, 50, and 51 were prepared by mixing the proper proportions of the morpholide of Example 47 and the morpholide of a fatty acid mixture which mixture of fatty acids was prepared by saponification and =acidulation of a cottonseed oil which had been selectively hydrogenated to an iodine value of 70.3 and a thiocyanogen value of 64.6.

The sample of Example 52 was prepared from cottonseed fatty acids which had been subjected to a dimerization treatment. A 46.5-gram sample of cottonseed fatty acids, 1.5 grams of water, and 2.0 grams of activated bleaching clay were placed in a flask equipped with a stirrer and reflux condenser. The mixture was heated at 230 C. for 4 hours, taken up in 50 ml. of commercial hexane, and filtered to remove the bleaching earth. Thehexane was removed by stripping under reduced pressure. The product, dimerized cottonseed acids, had a neutralization equivalent of 303. It was condensed with morpholine to form the motpholide of dimerized cottonseed acids by the procedure described in Example 47. The product was acid-free and had a nitrogen content of 3.66%.

The physical properties of the Vinylite VYDR resin plasticized with the morpholides of Exam-pies 47 to 52 are shown in Table V. The volatility losses were determined by the activated carbon method ASTM-D-LZOB- 5 2T.

The morpholide mixtures used in Examples 53 to 68 include binary and ternary compositions prepared by mixing appropriate proportions of the morpholide of the dimer acid used in Example 47, the morpholide of oleic acid, and the morpholide of palmitic acid. The compositions and the results of the plasticizer evaluation tests for these samples are given in Table VI. In Table VI, MD, MC, and MP represent the weight percent of the morpholides of dimer, oleic, and palmitic acids comprising the mixture, respectively.

We claim:

' 1. The mixture of morpholides of dimerized long chain fatty acids which acids consist essentially of dibasic acids containing from 32-44 carbon atoms and which dibasic acids result from the dimerization of C to C unsaturated fatty acids.

2. The mixture of morpholides of dimerized cot-tonseed oil fatty acids.

-3. The mixture of morpholides of dimerized long chain fatty acids which acids consist essentially of dibasic acids containing from 32-44 carbon atoms and which dibasic acids result from the dimerization of C to C unsaturated fatty acids and the morpholides of selectively hydrogenated cottonseed fatty acids which morpholides of selectively hydrogenated cottonseed fatty acids are prepared from saponiiied and acidulated cottonseed oil that has been selectively hydrogenated to reduce substantially all the polyunsaturates to monounsaturates, the total amount of saturates being maintained essentially unchanged.

.4. The mixture of'morpholides of dimerized long chain fatty acids which acids consist essentially of dibasic acids containing from 32-44 carbon atoms and which dibasic acids result from the dimerization of C to C unsaturated fatty acids and the morpholides of selectively hydrogenated cottonseed fatty acids which morpholides of selectively hydrogenated cottonseed fatty acids are prepared from saponified and acidulated cottonseed oil that has been selectively hydrogenated to reduce substantially all the polyunsaturates to monounsaturates, the total amount of saturates being maintained essentially unchanged, said morpholides of the dimerized long chain fatty acids and said morpholides of the selectively hydrogenated cottonseed fatty acids being present in the morpholide mixture in the ratio of about from 1 to 3 parts by weight of the former to 3 to 1 parts by weight of the latter. 1

5. A mixture of morpholides of oleic acid (MO), palmitic acid (MP), and dimer acids (MD), which dimer acids consist essentially of dibasic acids containing from 32-44 carbon atoms resulting from the dimerization of C to C unsaturated fatty acids, said mixture of morpholides being limited with respect to composition only to the extent that the weight fractionof MP based on the total Weight of the morpholide mixture is less than about 0.5 5

6. A mixture of morpholides of oleic acid (MO), palmitic acid (MP), and dimer acids (MD), which dimer acids consist essentially of dibasic acids containing from 32-44 carbon atoms resulting from the dimerization of C to C unsaturated fatty acids, said mixture of morpholides satisfying the following conditions with respect to composition, the weight fraction of MO based on the total weight of the morpholide mixture being greater than about 0.10 and the weight fraction of MP being between about 0.55 and 0.70.

References Cited by the Examiner UNITED STATES PATENTS 2,863,845 12/1958 Magne et al. 260-302 3,066,111 11/1962 Magne et a1 260'-30.4

OTHER REFERENCES Magne et al. (I); Some N-Disubstituted Amides of Long-Chain Fatty Acids as Vinyl Plasticizers; Industrial and Engineering Chemistry; vol. 50; 1958; pp. 617-618.

ALLAN LIEBERMAN, Acting Primary Examiner.

MORRIS LIEBMAN, Examiner.

L. T. JACOBS, Assistant Examiner, 

1. THE MIXTURE OF MORPHOLIDES OF DIMERIZED LONG CHAIN FATTY ACIDS CONSIST ESSENTIALLY OF DIBASIC ACIDS CONTAINING FROM 32-44 CARBON ATOMS AND WHICH DIBASIC ACIDS ARESULT FROM THE DIMERIZATION OF C16 TO C22 UNSATURATED FATTY ACIDS. 